Abstract Four PVC membrane electrodes for the determination of mebeverine hydrochloride (MvCl) were fabricated and fully characterized in terms of composition, life span, usable pH range, working concentration range and temperature. The membranes of these electrodes consist of mebeverinium-silicotungstate (Mv-ST), silicomolybdate (Mv-SM), phosphotungstate (Mv-PT), or phosphomolybdate (Mv-PM) ion-associations dispersed in PVC matrix with dibutyl phthalate plasticizer. The electrodes showed near-Nernstian response over the concentration range of 4.0 × 10 −6 to 1.0 × 10 −2 M MvCl and were applied to the potentiometric determination of mebeverinium ion in pharmaceutical preparations, serum and urine in steady state and flow injection (FI) conditions with average recoveries of 96.4–102 % and relative standard deviations of 0.132–1.86%. The electrodes exhibit good selectivity for MvCl with respect to a large number of inorganic cations, organic cations, sugars and amino acids. The sensitivities of these electrodes are high enough to measure as low as 1.86 μg/ml of MvCl which permit the determination of the K sp values of the ion-associates used. The proposed potentiometric methods offer the advantages of simplicity, accuracy, automation feasibility and applicability to turbid and colored sample solutions.